GB2184450A

GB2184450A - Reversible temperature-indicating compositions

Info

Publication number: GB2184450A
Application number: GB08531817A
Authority: GB
Inventors: Tsutomu Kito; Norikazu Nakasuji; Takashi Kataoka; Hiroshi Inagaki; Yutaka Shibahashi; Nobuaki Matsunami
Original assignee: Pilot Ink Co Ltd
Current assignee: Pilot Ink Co Ltd
Priority date: 1984-06-26
Filing date: 1985-12-24
Publication date: 1987-06-24
Also published as: DE3545813A1; US4732810A; FR2592158B1; JPH0129398B2; GB2184450B; DE3545813C2; FR2592158A1; GB8531817D0; JPS619488A

Description

1 GB 2 184 450 A 1

SPECIFICATION

Reversible temperature-indicating compositions This invention relates to reversible temperature-indicating compositions having as a main component one or 5 more compounds selected from esters having a certain range of AT va I ues [melting point ('C) -clouding point ('C)], and characterized by an extremely narrow hysteresis margin in their colour density - tem perature curves.

The conventional reversible temperature-indicating compositions include those materials utilizing the thermochromatic properties of meta I I ic complex salts such as A92H9214 and CU2H914. Another example of a 10 traditional material is cholesterol I iquid crystal.

However, these materials have been found universally unacceptable in practical application because of the following problems.

(1) Metallic complex salts exhibita verywide margin of hysteresis, that is,theydo not provide the decolor ing effecton reversal atthe precise temperature range asthat atwhich colorwas previously developed.This 15 hysteretically unstable fluctuation has disqualified them forapplication in temperature-indicating instru mentssuch asthermometers.

0The metalliccomplex salts and cholesterol liquid crystal provide avery limited selection ofavailable chromatic varieties. In the industrial application of metallic complex salts, onlytwo versions ofreversible colorchange are available,from yellowto orange and red to black. As for cholesterol liquid crystal, practical 20 use is limited almosttothe reversible colorchanges brown to orfrom green and green to orfrom blue, dueto an optical reaction.

(3) These conventional materials suffera considerable limitation in processing, for example, liquicicrystal display. Acholesterol liquid crystal reversible temperature indicating material requiresthe incorporation ofa blacksubstrate layerto ensuresuitable coloring byoptical reaction,which adds extra manufacturing cost. 25 Further, since it must be kept in completely sealed condition to protectagainst undesired effects ofrnoisture and humidity, considerable limitations are imposed notonly on storage and transport, but also practical application. Metallic complex salts impose grave limitations on preparation ofthe matrixthrough whichthe material is uniformly distributed.

Itis an aim ofthe present invention to provide a reversible temperature indicating material which hasa 30 hysteresis range (AH) sufficiently narrowto be suitable as atemperature indicating material forthermo meters; which exhibits a wide range ofthromatic varieties; and which imposes minimum limitationson industrial preparation.

The aim ofthe present invention is achieved bytheaddition ofone or moreselected estercompounds having a certain particular range ofATvalues as a main component so thatthe resultant prepared composi- 35 tion provides a desired level of AH.

According to the present invention there is provided a reversible temperature-indicating composition com prising:

(A) at leastone electron-donating chromatic organic compound selectedfrom diaryl phthalides, indolyl phthalides, polyary] carbinols, leuco auramines, acryl auramines, aryl auramines, Rhodamine B lactams, 40 indoles, spiropyrans and fluorans; (B) at least one compound selected from phenolic compounds having 6 to 49 carbon atoms, metal salts of the phenolic compounds, aromatic carboxylic acids having 7 to 12 carbon atoms, aliphatic carboxylic acids having 2 to 5 carbon atoms, metal salts of carboxylicacids having 2 to 22 carbon atoms, acidic phosphoric esters having 1 to 44 carbon atoms, metal salts ofthe acidic phosphoric esters and triazoie compounds having 2 to 24 carbon atoms; and (C) at least one ester compound selected from following compounds having a ATvalue [melting pount ('C) - clouding point ('Q in the range 3'C or less: branched alkyl esters and arylalkyl esters ofstraight-chain saturated aliphatic carboxylic acids, and alkyl esters of aliphatic carboxylic acids having one or more of double bonds, branched alkyl groups, hydroxyl groups, carbonyl groups and halogen atoms in the carbon so chain, said components (A), (B) and (C) being present in a weight ratio in the range of 1: 0.1 to 50: 1 to 800 and being in a form of homogeneous fused mixture.

The present invention is based on the discovery thatthe deviation ofthe decoloring temperature from the coloring temperature orthe hysteresis margin (AH) has a close correlation with the ATvalue ofthe ester group component; and, in particular, that, when the ATvalue ofthe one or more ester compounds constitut- 55 ing Component (C) is not higherthan YC, the reversible temperature indicating composition has a desirably minimum hysteresis margin.

In the composition, components (A), (B) and (C) are mixed in a desired ratio that is determined accordingto the type of hue and the color-developing and decoloring temperature required. The desired coior, color density, and decoloring temperture ofthe reversible temperature indicating composition are variously ob- 60 tained by selective combination ofthe components (A), (B) and (C),which function to determine hue, color densityand color/decoloring temperature respectively.

As the component (C), any ester compound may be applicable, provided that its ATvalue is notgreater than 3'C, more preferable 2.5T, regardless ofthe molecularweight ofthe ester or whatever functional group or substituent other than the ester radical or ester radical maybe present. The inclusion of one or more such 65 2 GB 2 184 450 A 2 ester compounds, it has been proved, can provide in the reversible temperature indicating composition of the present invention a desired variety of temperature indicating characteristics in the temperature range of approximately from -80'Cto +1OWC.

In the accompanying drawing:

Figure 1 illustrates graphicallythe relationship between change in colordensityand temperature plottedto 5 indicatethe hysteresis characteristic of the reversible temperature indicating composition according tothe present invention.

Figure2 illustrates graphically a similar relationship indicating the hysteresis characteristic of the prior known reversible tem peratu re-indicati ng materials.

Inthe graphsof Figures 1 and 2,temperature is plotted on abscissa whilethe color density is plotted onthe ordinate. Thevarious symbols are defined asfollows:

is T1, Tl': T2, T2': T3, T3':

temperature level atwhich complete coloring takes place. range of transition temperature. temperature level atwhich complete decoloring takes place.

Cl C2, Cl'C2': difference of color density atthe same temperature level between coloring and decoloring cycles. hysteresis margin.

AH, AW:

V_ A Figure 3 is a scatter diagram plotted to illustrate the correlation of hysteresis margin AH ('C), taken along the ordinate, with different values of AT ('C), taken along the abscissa, of the ester corn pound i n the reversi ble temperature indicating composition according to the present invention.

Thus, Figu re 3 illustrates g raphical ly the relationship between the AT va lue of the one or more ester com- 25 pounds forming Component (C) and the AH range of the composition. Study of Figure 3 obviously shows a close correlation between the ATvalue and AH margin. Fu rther study shows that, when the ester compou nds additionally have a AT val ue of not hig her than WC the resultant reversible temperatu re-indicating corn posi tion has a desirably minimum H margin.

Thus, by calculating the ATvalue of any given ester compounds the AH range of the composition can be 30 predicted. This eliminatesthe conventional inconvenience in which computation of the AH range hasto be done afterthe composition has actually been prepared.

These ester compounds listed above as having individually or in combination as desired ATvalue can easily be preparedfrom an extremely extensive range of acids and alcohols.

The ratio of each ingredient in the composition varies depending on the desired color strength, the color- 35 ing temperature,the mode of colorchange, and thetypes of constituent compounds. However, ourstudies haveshown thatthe desired characteristics are achieved from the combination comprising byweight 1 part of component (A),from 0.1 to 50, and more preferably 0.5to 20 parts of component (B), and from 1 to 800and more preferably 5to 200 parts of component (C).

Each of components (A), (B) and (C) can be constituted bytwo or more compounds selected from each defined category, suitably mixed. The composition may also contain suitable amounts of anti-oxidant, ultra violet light absorbent, solubilizer, thinner, and/or intensifier.

In addition, the composition of this invention can contain auxiliary agents such as alcohols, amides, ket ones, and/orsulfides, if required, as long asthey do not affectthe hysteresis characteristic of the contained estercomponent (C). It is importaritto note, however, thatthese additives tend to expand the hysteresis range, if theirtotal ratio byweight exceed 50% of the ester component (C). Accordingly, it is preferred to limit theirinclusion belowthis limit.

As illustrated in Figure 1,the reversible temperature-indicating composition of the present invention shows a very narrow range of hysteresisto changes of temperature; in repeated coloring and decoloring as the temperature changes. Referring to the curve of Figure 1, A indicatesthe point of complete decoloration 50 while B the point of full coloration, attemperatures T3 and T1, respectively, Cl and C2 are respectively curve portions plotted to indicate their transition ranges of coior density gradient in the coloring and decoloring cycles. AH isthe hysteresis margin at midpoint in thetransition ranges indicating howthe color densityon increase of temperature differs from that on decrease atthe sametemperature T2. Itfollows accordinglythat the closerthe curve portions Cl and C2,the narrowerthe hysteresis margin thus ensuring a more precise temperature indication.

Further, it has been proved as a result of experiments thatthe content of ester compounds in component (C) with the ATvalue of not higherthan WC enables the resulting reversible temperature indicating composi tion to exhibit a desirably low AH margin of lessthan 30C, ensuring a mono-temperature/mono-state relation ship giving a satisfactorily visible reading. A still better relationship is provided if the ATvalue is not higher 60 than 2.5'C.

Figure 2 indicates the temperature-to-color density curve plotted to indicate the typical AH margin in the prior known reversible temperature indicating material. It is obvious from the study of Figure 2 thatthe materials are not capable of accurate temperature indication since the color density thereof exhibits two distinctively different conditions at a particulartemperature within the color changeable region. Those con- 65 3 GB 2 184 450 A ventional materials normally contain organic compounds having a ATvalue of from about 3'C to abut WC, thus expanding the hysteresis marginAH and differentiating their characteristics from the desired accurate temperature indicating characteristic assured by the mono- temperature/mono-state relationship achieved by the present invention.

The components (A), (B) and (C) will be described in full detail.

Examples of the electron-donating chromatic organic component (A) are asfollows:

Crystal Violet lactone, Malachite Green factone, Michler's hydrol, Crystal Violet carbinol, Malachite Green Carbinol, N -(2,3-dich 1 o ro phenyl) leucoauramine, N-benzoyl auramine, Rhodamine B lactams, N-acetyl auramine, N-phenyl auramine, 2-(phenyl irn in oethyl iden e)-3,3-d i methyl indoline, W3,3trimethlidolinobenzospiropyran, 8-methoxy-N-3,3trimetylindolinobenzospiropyran, 3-diethylamino-6methyl-7-chlorofluoran, 3-dimethylamino-7-methoxyfluoran, 3-diethyl-amino-6-benzyioxyfluoran, 1,2benz6-cliethylfluoran, 3,6-di-p-toluidino-4,5-dimethyifiuoranphenylhydrazide--Y-Iactam, 3-amino-5-methylfluoran, 2-methyl-3-amino-6,7dimethylfiuoran, 2,3-butylene-6-di-n-butylaminofluoran, 3diethylamino-7anilinofluoran, 3-diethylamino-7-(p-toluidino)fluoran, 7-acetoamino-3diethylaminofluoran, 2-bromo-6-cyclohexylaminofluo ran and 2,7-dichloro-3-methyl-6-n- butylaminofluoran.

Compounds allowable ascomponent (B) may be selected from thefollowing groups (a) to (g).

(a) Phenolic hydroxides, both monophenolicand polyphenolic compounds, including phenols substituted with alkyl, aryl, acyl and alkoxycarbonyl groups and halogen atoms.

Examples of these compounds are asfollows:

Tert-butylphenol, nonylphenol, dodecylphenol, styrenated phenols, 2,2methylene-bis(4-methyi-6- tertbutylphenol), et-naphthol, P-naphthol, hydroquinol monomethylether, quaiacol, eugenol, p chlorophenol, p-bromophenol, o-chlorophenol, o-bormophenol, o- phenylphenol, p-(p-chlorophenyi) phenol, o-(o-chlorophenyi)-phenol, p-methyl hydroxybenzoate, p-ethyl hydroxybenzoate, p-propyl benzoate, p-butyi hydroxybenzoate, p-octyl hydroxybenzoate, p-dodecyl hydroxybenzoate, 3-iso-propyi catechol, p-tert-butyl-catechol, 4,4-methylene-cliphenol, 4,4-thio-bis(6- tert-butyl-3-methyi phenol), 1,1 -bis(4hydroxyphenyl)-cyclohexane, 4,4-butylidene-bis(6-tert-butyi-3-methyl phenol), bisphenol A, bisphenol S, 1,2-dioxyna phtha fen e, chlorocatechol,'4romocatechol, 2,4- dihydroxybenzophenone, phenol phthalein, o cresolphthalein, methyl protocatechuate, ethyl protocatechuate, propyl protocatechuate, octyl proto catechuate, dodecyl protocatechuate, 2,4,6-trioxym ethyl benzene, 2,3,4- trioxyethyl benzene, 2,3,4 trioxyethyl benzene, methyl gal licate, ethyl gallicate, propyl gallicate, butyl gallicate, hexyl gallicate, octyl 30 gallicate, dodecyl gallicate, cetyl gallicate, stearyl gallicate, 2,3,5- trioxynaphthalene, tannic acid and phenol resins.

(b) Metal salts of the phenolic hydroxides, the metal being any selected from sodium, potassium, lithium, calcium, zinc, zirconium, aluminium, magnesium, nickel, cobalt, tin, copper, iron, vanadium, titanium, lead and molybdenum.

(c) Aromatic carboxylic acids and aliphatic carboxylic acids having 2to 5 carbon atoms consisting of maleic acid, fumaric acid, benzoic acid, toluic acid, p-tert-butyl benzoic acid, chlorobenzoic acid, bromobenzoic acid, ethoxy benzoic acid, gallicacid, naphthoicacid, phthalic acid, naphtha lene-dica rboxyl!c acid, aceticacid, propionic acid, butyricacid and valericacid.

(d) Metal salts of carboxylic acids, both monocarboxylic and polycarboxylic, the following being samples 40 of the acids:

Acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, behenic acid, crotonic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, monochforoacetic acid, monobromoacetic acid, monofluoracetic acid, glycolic acid, hydroxy- propionic acid, hydroxybutyric acid, ricinoleic acid, 12-hydroxy-stearic acid, lactic acid, pyruvic acid, oxalic 45 acid, malonic acid, succinic acid, adipic acid, sebacic acid, malic acid, tartaric acid, valeric acid, maleic acid, fumaric acid, naphthenic acid, benzoic acid, toluic acid, phenyl acetic acid, p-tert-butyl-benzoic acid, cin namic acid, chlorobenzoic acid, bromobenzoic acid, ethoxybenzoic acid, mandelic acid, protocatechuic acid, vanillic acid, resorcyclic acid, dioxybenzoic acid, dioxychlorobenzoic acid, gallic acid, naphthoic acid, hydroxynaphthoic acid, phthalic acid, monoethylester or phthalic acid, naphthalene-dicarboxylic acid, monoethylester of naphthalene dicarboxylic acid, trimellitic acid and pyromellitic acid (the salt-forming metals being any selected f rom sodium, potassium, lithium, calcium, zinc, zirconium, aluminium, magnesium, nickel, cobalt, tin, copper, iron, vanadium, titanium, lead and molybdenum.

(e) Alkyl esters, branched alkyl esters, alkenyl esters, alkyl esters, cycloalkyl esters, and aryl esters of acidic phosphoric compounds and their derivatives, both monoesters and diesters, ortheir combinations (acidic 55 phosphates), are exemplified below:

Methyl acid phosphate, ethyl acid phosphate, n-propyl acid phosphate, nbutyl acid phosphate, 2-ethyl hexyl acid phosphate, n-octyl acid phosphate, isodecyl acid phosphate, n- decyl acid phosphate, iauryl acid phosphate, myristyl acid phosphate, cetyl acid phosphate, stearyl acid phosphate, docosylacid phosphate, oleyl acid phosphate, 2-chloroethyl acid phosphate, 2,3-dibromo-2,3- dichloropropyl acid phosphate, dichloropropyl acid phosphate, cyclohexyl acid phosphate, phenyl acid phosphate, o-toly] acid phosphate, 2,3-xylyl acid phosphate, p-cumenyl acid phosphate, mesityl acid phosphate, l -naphthyl acid phosphate, 2-naphthylacid phosphate, 2-anthryl acid phosphate, benzyl acid phosphate, phenethyl acid phosphate, styry] acid phosphate, cinnamyl acid phosphate, trityl acid phosphate, phenyImethyl phosphate, phenylethyl phosphate, phenyl n-propyl phosphate, phenyl n-butyl phosphate, phenyl n- octyl phosphate, phenylauryi 65 is 4 GB 2 184 450 A 4 phosphate, phenylcyclohexyl phosphate, phenyl (2,3-xylyl) phosphate, cyclohexylstearyl phosphate, cyclo hexylcetyl phosphate, dimethyl phosphate, diethyl phosphate, di-n-propyl phosphate, di-n-butyl phosphate, di-n-hexyl phosphate, di(2-ethylhexyl) phosphate, di-n-decyl phosphate, dilauryl phosphate, dimyristyl phosphate, dicetyl phosphate, distearyl phosphate, dibehenyl phosphate, diphenyl phosphate, dicyclohexyl phosphate, di-o-tolyl phosphate, bis(tri phenyl-m ethyl) phosphate, bis (diphenyl methyl) phosphate, di(2,3- 5 xylyl) phosphate, dibenzyi phosphate and di(l -naphthyi) phosphate.

(f) Metal salts of the above g roup (e), the metal being selected from sodium, potassium, lithium, calcium, zinc, zirconium, aluminium, magnesium, nickel, cobalt,tin, copper, iron, vanadium, titanium, lead and molybdenum.

(g) Triazole compounds including 1,2,3-triazole, 4(5)-hydroxy-1,2,3triazole, 5(6)-methyi-1,2,3 benzotriazole, 5-chloro-1,2,3-benzotriazole, 7-nitro-1,2,3-benzotriazole 4-benzoylamino-1,2,3-benzotriazole, 4-hydroxy-1,2,3-benzotriazole, naphtho-1,2,3-triazole, 5,5'-bis(1,2,3benzotriazole) and 1,2,3-benzotriazole-4 sulfooctylamide.

Examples of estercompounds available as component (C) are asfollows:

2-ethyihexyl acetate, 2-ethylhexyl behenate, 2-ethylhexyl myristate, 2ethylhexyl caprate, 3,5,5 trimethylhexyl laurate, 3,5,5-tri methyl hexyl myristate, 3,5,5-tri methyl hexyl palmitate, 2-methylbutyl cap roate, 2-methylbutyl caprylate, 2-methylbutyl caproate, 1-ethylpropyl palmitate, 1-ethylpropyl stearate, 1-ethylpropyl behendate, 1-ethylhexyl laurate, 1-ethylhexyl myristate, 1 - ethyihexyl palmitate, 2 methylbenzyl caproate, 2-methyl benzy] caprylate, 2-methyl-benzyl caproate, 2-methylbenzyl laurate, 2 methy[butyl stearate, 3-methylbutyl behenate, 1 -methylheptyl stearate, 1 -methyl-heptyl behenate, 1 ethylpentyl caproate, 1-ethylpentyl palmitate, 1-methylpropyl stearate, 1- methyloctyl stearate, 1-methylhexyl stearate, 1, 1 -di methyl propyl laurate, 1-methyi-pentyi caprate, 2-methylhexyl stearate, 3 phenylpropyl stearate, 2-methylhexyl behenate, 3,7A i methyl octyl laurate, 3,7-d i methyl octyl myristate, 3,7 dimethyloctyl palmitate, 3,7-dimethyloctyl stearate, 3,7-di methyl octyl behenate, n-butyl erucate, 3,7 dimethyloctyl erucate, isostearyl erucate, steary] isostearate, cetyl isostearate, 2-methylpentyl 12-hydroxystea rate, 2-ethyihexyl 18-bromostearate, isostearyi 2-keto myristate, 2-ethylhexyl 2 fluorostearate,stearyl oleinate, behenyi oleinate, stearyl linolate and behenyl linolate.

In practical application,the reversible temperature indicating compositions according tothe present in vention may be used in a pulverized or molten state. However,they may moreefficiently be handled in microcapsules, preferably having a diameter of 30 Lm or less. Encapsulation can be effected byany known 30 method such as coacervation, interfacial polymerization, in situ polymerization orspray drying. The com position in theform of microcapsules can be applied in the same manner as in conventional practiceto plastics, rubber material orthe surfaces of other materials, oras printing ink, paint, pen inkorspraying material.

The composition according tothis invention and microcapsules containing itwill now be described in part- 35 icular Examples thereof. It isto be understood, however,thatthe present invention should not be limitedto the Examples given.

In the Examples, electron-donating chromatic organic compoundsto be mixed intothe composition are referredto in abbreviatedform as CFsfollowed by a different number (e.g., CF-1, CF-2, and so on). Their respective identifications represented bychemical consttitution, are given together later in the specification. 40

Determination of melting and clouding points, from which the ATvaluewas calculated, was performed using melting point measuring apparatus of a type automatically measuring variation of transmittance of a sample in terms of temperature. The melting pointwastaken asthe temperature atwhich thesample reached the completely molten state. Everyvalue in the obtained test data wasthe mean of three measured samples.

Further, determination of AH was based on the difference of color densities (represented by C, andC2in Figure 1) at the same temperature T2, using a color-difference meter.

is Example 1

A mixture composed of 2 g of CF-1, 6g of 2,2-bis(4-hydroxyphenyi)pentane, and 50 g of 3,5,5-tri methyl hexyl stearate was heated until it melted into a homogenous state and then encapsulated by a known co acervation process into microcapsules containing the reversible temperature indicating composition of this invention. 50 9 of the microcapsules thus produced were uniformly dispersed into a vehicle which comprised g of water, 200 g of copolymerized ethylene-vinyl acetate emulsion (negatively charged, pH of 4.5to 5.5, viscosity of 2,000 cps at30'C, and solids content of 50%) and 10 g of sodium alginate. A 50 micron thickfilm of polyester was screen printed with the resultant product, and the printed area was laminated with a 12 micron thick polyesterfilm to obtain a temperature indicating material. The printed film wasthen cooled to 2'C until fully colored in magenta, and leftto stand at a temperature of WC, amid point in the transition stage of the coloring gradient (or in the range between T1 and T3 in Figure 1), atwhich the film showed a color density C2. Subsequently,the film was heatedto 2WC, atwhich colorfaded completely, followed bycooling 60 and maintaining it at8'C, atwhich it showed a color density C,. C, was determined as 7.2 while C2was6.6; both colours lookedto the eyejust as suggested bytheirvalues.

The procedure was repeated with similarsamples and their colorvalue determined. The results obtained were substantially the same as above.

The ATvalue of the 3,5,5-trimethyhexyl stearate was 1.5'C and the AH value of the reversible temperature 65 %1 i I- 1 GB 2 184 450 A indicating composition was 2.3'C.

4 10 h Example2

A mixture of 5 g of CF-2,12 g of p-cumylphenol, and 100 g of 2methylhexyl palmitatewas heated until it melted into a homogenous state, and encapsulated by a known interfacial polymerization method into microcapsules containing the reversible temperature indicating composition. Then 80 g of the microcapsules thus produced were uniformly dispersed into a vehicle consisting of 200 g of polymerized esteracrylate emulsion (negatively charged, pH of 4, viscosity of under 150 cps, and solids content of 31%),4 g of sodium alginate, and 0.5 g of cross-linking agent. A cotton cloth was printed with the resultant product andthen cooled to -20T until the pattern was colored green. Then,the printed cloth was leftto stand at atemperature 10 of -1 2'C, a level in the transition zone of the coloring gradient atwhich it showed a color density Cl. Then said cloth was exposed to a varying temperaturefrom WC,the level atwhich the printwas supposedto completely decolor,to -12A and maintained at -1 2'C, atwhich it showed a color density C2. Cl and C2were measured and determined as 7.2 and 6.6, respectively, and appeared almost equivalentto the eye. The procedure was repeated with similar samples and their color value measured. The results were substantially 15 the same as the readings above.

The AT value of the 2-methylhexyl pal mitate was 1.40C and the AH va 1 ue of the reversible tern peratu re indicating composition was 2.1'C.

Example 3

A mixture consisting of 6 g of CF-3,189 of a zinc salt of bisphenol A, 40 g of 3-methylbutyl behenate, and 60 g of 2-methylbutyl behenate was heated until it melted into a homogenous state, and then encapsulated by a known spray drying method into microcapsules containing the reversible temperature indicating composition of this invention. Then, 80 9 of the microcapsules thus produced were dispersed into a vehicle consisting of 20 g of copolymerized styrene-maleic acid anhydride, 5 9 of 25% aqueous ammonia solution, and 0.5 9 of antifoaming agentto give an aqueous photogravure ink.

A 20 micron thick synthetic paper of polystyrene was printed by a photogravure method with the inkthus produced, and then coated with a thin film of styrene resin overthe printed surfaceto give atemperature indicating label. The resultant label was immersed into a vessel of water heated at WC until the printwas completely decolored, and then left immersed in a vessel of water heated at WC, a level in thetransition zone 30 of the coloring gradient, atwhich it showed a color density Cl. Subsequenly, the label was leftto stand and cooled to room temperature, followed by heating and maintaining at WC, atwhich itshowed a colordensity C2. Comparison gave almost no difference of color strength between Cl and C2.

The ATvalue of the 3-methylbutyl behanatewas 1.40C, the ATvalue of 2methylbutyl behanatewas 2.90C and the AH value of the reversible temperature indicating composition was 2.WC.

In addition, following the preparation method of Example 1, the different versions of reversible temperature indicating composition were prepared and tested. The results, together with the measured values of AT and AH, are presented in the Table.

0) Table

AT AH Temperature CC) Reversible temperature indicating composition value value Colorat Colorat of of below above Example compo- compo- coloring coloring No. Component(A) Component(B) Component (C) nent (C) sition temperature temperature 4 CF-4 (6g) 5-nitro-1,2,3- 2-ethylhexyl 2.0 3.0 -30 benzotriazole caprate (100) Vermillion Decolored (1 5g) CF-5 (4g) p-octylphenol 1-ethylpropyl 2.3 3.0 42 (20g) behanate (1 00g) Pink Decolored 6 CF-6 (2g) Bis(4-hydroxy- Stearyl erucate 1.9 2.5 38 phenyl) sulfone (1 00g) Black Decolored (5g) 7 CF-7 (6g) 2,3-xylyl acid 3-phenyl propyl 1.5 2.0 18 phosphate (1 5g) stea rate (1 00g) Darkred Decolored 8 CF-8 (8g) 4-hydroxy- IDL-2-methylbutyl 2.4 3.8 15 stearyl stearate Orange Decolored benzoate (1 6g) (100g) 1 T M m N) C0 Abl P. (n C 0) 7 GB 2 184 450 A 7 1, 10 The electron-donating chromatic organic compounds referred to in the Examples areas follows:

CF-1: 3-d iethylam i no-7,8-benzof 1 uora n CF-2: 6'-(diethylamino)-2'[cyclohexyi(phenyimethyl)-aminol-spiro[isobenzofuran-1 QH), g'(9H)xanthen]-3-one CF-3: 2'-[(4-n-butylphenyi)aminol-3'-methyi-6'(diethylamino)-spiro[isobenzofuran-1 (3H),9'(9H)xanthen]-3-one CF-4: 3diethylamino-5-methyi-7-dibenzyl-aminofluoran CF-5: 3,3'-bis(l-ethyl-2methyl-l H-indol-3-)-1(3H)-isobenzofuranone CF-6: 6'(cyclohexyimethylamino)-3'-methyi-2'-(phenylamino)-spirolisobenzofuran-1 (3H), 9(9H)xanthen]-3-one CF-7: 2'-[bis(ph enyl m ethyi)a m in ol -Xmethyl -6'-(d i ethyl am i no)-spi rol iso benzofu ra n- 1 (3H), 9'(9H)xanthen]-3-one CF-8: 3-chlor-6-cyclohexylaminofluoran It wi I I be clear from the above description that the present invention provides improved reversible tem- perature indicating compositions capable of coloring in a wide variety of hues and at a wide range of different temperatures. Particularly, the compositions of this invention have an extremely marked advantage, which has hitherto been unobtainable with conventional reversible temperature recording materials, in that they color at or very close to the temperature at which they decolor. Further,they exhibit very similar colorstren gths, whether on increase or decrease of temperature.

With conventional compositions, the hysteresis range (AH), factor that determines the temperature indica tion performance, can only be computed on the finished product. However, the present invention permits preparative estimation of this hysteresis value based on determination of the AT value of the component ester compounds; thus, the hysteresis range can be controlled depending on the purpose for which the product is intended. This contributes to enhancing the efficiency of production. Further, as there are num erous ester compounds with ATvalues in the effective range, suitable combination can provide a variety of reversible temperature indicating compositions having different response temperatures.

Also, the composition according to this invention is capable of being repeatedly colored and erased at a fixed temperature. Thus, it can be embodied as am ulti-colortemperature indicator in which differentforms of the composition are used to provide a different color at various levels of temperature. This invention may 30 be applied in the multi-color printing of printed patterns, in two or more variations of the composition cap able of changing from one color to another with changes of temperature. Such a pattern can also be printed for decorative purposes on T-shirts, ties, towels, gloves, training wear, blouses, skiing wear; for decorative or interesting effects on wal I paper or pictures; or for tempertureindication on packages or labels for contents which are subject to a change of quality with temperature. In addition, since the compositions of the present 35 invention have a very narrow hysteresis range (,LH), their application as multicolortemperature indicators provides enhanced performance, compared with the conventional reversible temperature indicating com position having wide hysteresis ranges; in particular the compositions of the present invention allow de tailed readings within smal I temperature ranges, providing accurate measurement with a wide variety of hues. It will be appreciated thatthe present invention contributes not only in the field of thermometers but also enables increased usefulness and convenience to be achieved in other industrial applications.

Claims

1. A reversible tem peratu re-inclicating composition corn prising:

(A) at least one electron-donating chromatic organic compound selected from diaryl phthalides, indoly] phthalides, polyaryl carbinols, leuco auramines, acryl auramines, aryl auramines, Rhodamine B lactams, indoies, spiropyrans and fluorans; (B) at least one compound selected from phenolic compounds having 6to 49 carbon atoms, metal salts of the phenolic compounds, aromatic carboxylic acids having 7 to 12 carbon atoms, aliphatic carboyxlic acids 50 having 2 to 5 carbon atoms, metal salts of carboxylic acids having 2 to 22 carbon atoms, acidic phosphoric esters having 1 to 44 carbon atoms, metal salts of the acidic phosphoric esters and triazole compounds having 2 to 24 carbon atoms; and (C) at least one ester compound selected from following compounds having a ATvalue [melting point (T) - clouding point ('Q in the range 3T or less: branched alkyl esters and arylalkyl esters of straight-chain saturated aliphatic carboxylic acids, and alkyl esters of aliphatic carboxyUc acids having one or more of double bonds, branched alkyl groups, hydroxyl groups, carbonyl groups and halogen atoms in the carbon chain, said components (A), (B) and (C) being present in a weight ratio in the range of 1: 0.1 to 50: 1 to 800 and being in a form of homogeneous fused mixture.

2. A composition as claimed in Claim land contained in microcapsules having a diameter of 30 lim or 60 less.

3. A composition as claimed in Claim 1 or 2, in which said components (A), (B) and (C) are present in a weight ratio of 1: 0.5 to 20: 5 to 200.

4. A composition as claimed in any preceding claim, in which the one or more ester compounds constitut ing component (C) have a ATvalue of not greaterthan 2.50C.

8 GB 2 184 450 A

5. A composition as claimed in Claim land substantially as herein described.

6. A reversible temperature-indicating composition substantially as hereinbefore described with referenceto anyone of foregoing Examples.

7. An article comprising a substrate bearing on a surface thereof a layer of a composition as claimed in 5 any preceding claim.

8. Atemperature-indicating instrument incorporating one or more compositions as claimed in anyone of Claims 1 to 6.

9. The features as herein disclosed, or their equivalents, in any novel patentable selection.

Printed for Her Majesty's Stationery Office by Croydon Printing Company (U K) Ltd,5187, D8991685. Published by The PatentOffice,25Southampton Buildings, London WC2A lAY, from which copies maybe obtained.

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